Aqueous germicidal composition containing alkyl phenols



N'lED STATE" PArENr OFF! AQUEOUS GERMCIDAL COMPOSITION CONTAINING ALKYLPHENOLS Reuben Schuler, Elizabeth, N. a, assignor to Stance IncorporatedNo Drawing.

Application June 29, 1933,

Serial No. 678,191 r 4 Glaims. (CL 167-31) This invention relatesto thepreparation of improved antiseptic compositions and more particularly tothe use of oil soluble emulsifying agents with alkyl phenols which aresubstantially insolu or more carbon'atoms are especially powerful, but

are substantially insoluble in water. Germicidal compositions preparedheretofore with such alkyl phenols have consisted of solutions of thephenol in suitable organic solvents or in aqueous solutions containinglarge amounts of mutual solvents such as glycerine. It is necessary touse such so.-

lutions in concentrated form as they precipitate out the alkyl phenol ondilution with even relatively small amounts of water.

It hasnow been found that highly effective antiseptic compositions whichretain their effectiveness on dilution with even 50 to 100 or more partsof water may be prepared with these alkyl phenols. Such compositionsconsist of a solution of the alkyl phenol in a-solvent medium containingalso in solution an effective emulsifying or dispersing agent. Theessential characteristic of 30 these new compositions appears to betheir ability to permit dilution with even large amounts of waterwithout appreciable formation of any separate phase; that is, thediluted compositionsremain clear and show little or no turbidity orcloudiness, even on standing for long periods of time. Since these alkylphenols are known to be insoluble in the concentrations present in suchdiluted aqueous compositions, it is believed that the lattercompositions represent colloidal solutions in which the germicide ispresent in an extremely finely divided'form.

Among the alkyl phenols suitable for this invention are incuded thebutyl, amyl, hexyl, heptyl phenols, cresols, resorcinols, pyrogallols,and other alkylated phenols and homologs of phenols including hydroxyaromatics containing condensed nuclei such as naphthols. Normal and iso,primary, secondary and tertiary alkyl phenols are included. Secondaryand tertiary alkyl phenols are those in which the carbon atom of thealkyl group connected to the aromatic nucleus is also connected to twoor three other alkyl carbon atoms respectively. Poly alkyl phenols suchas (ii-tertiary butyl resorcinol, di-isopropyl phenol, and the like arealso included. Mixtures of alkyl phenols prepared by reaction of aphenol with a petroleum fraction containing olefines of about three toten carbon atoms, preferably in the presence of relatively large amountsof concentrated sulfuric acid, are especially effective.

The emulsifying agents suitable for this invention are those which aresoluble in oil and which cause formation of oil in water emulsions ondilution of an oil solution thereof with large amounts of water.

The oil soluble sulfonates obtained in the refining of petroleum oilswith strong or fuming sulfuric acid are an example of such emulsifyingagents. The sulfonates should be preferably in a highly purified formsubstantially free from uncombined sulfuric acid, hydrocarbon oils,inorganic salts and asphaltic or tarry matter. It is recognized that oilsoluble sulfonates of widely varying characteristics may be obtainedfrom the different refining operations in use in the petroloum industry.The sulfonates preferred for this invention are those of the readilyemulsifiable type; that is, those sulfonates which when dissolved in oilin concentrations of about 5% produce miscible oils which are readilydispersable in water, with simple agitation.

The mutual solvents suitable for this invention are those which dissolvesubstantial amounts'of both the alkyl phenols and the emulsifyingagents,and are also soluble in water. Such mutual solvents are the loweralcohols such as methyl, ethyl and isopropyl alcohols, the water solubleketones, such as acetone, and other similar oxygenated organic compoundsof relatively low molecular weight such as ethyl acetate.

The following examples represent highly effective germicidalcompositions which may be prepared according to this invention.

Example 1 Two parts of secondary hexyl phenol and five parts of,oilsoluble sodium sulfonate are dissolved in ninety-three parts of 91%strength isopropyl alcohol. One part of this solution mixed withforty-nine parts of water yields a clear transparent solution which isstrongly antiseptic, killing Staphylococcus aureus in five minutes, astested by the Food and Drug Administration method, published in theUnited States Department of Agriculture Circular 198, of December 1931.

parts of oil soluble sodium sulfonate are dissolved in eighty-six partsof 91% strength isopropyl alcohol. One part of this solution mixed withup to 160 parts of water yields a clear solution which shows a veryfaint indication of cloudiness. This solution also kills Staphylococcusaureus in five minutes by the test mentioned in Example 1.

These compositions may be used for sterilization of buildings,instruments, bedding and clothlu ing, for application to woundsgenerally, and as a personal antiseptic. Suitable perfumes and flavors,such as sugar, glucose, syrup, and the like may be added as desired. Itis generally preferable to exclude oils, particularly hydrocarl5 bonoils, from such compositions. The alkyl phenols appear to bepreferentially soluble in such oils, and larger amounts of alkyl phenolsare required to produce effective germicides if substantial amounts ofoil arepresent.

21) The oil soluble sulfonates used in the above examples are preparedbythe following method: A petroleum oil fraction suitable for thepreparation of medicinal white oils is treated with an excess of fumingsulfuric acid. The resulting sludge is allowed to settle and isseparated from the oil. The remaining upper layer of oil is neutralizedwith an alkali such as caustic soda or sodium or potassium carbonate orammonia and is simultaneously or thereafter mixed with an aqueousalcohol. The alcoholic solution is then allowed to settle and isseparately drawn off. It contains oil-soluble sulfonates and also someinorganic salts and oil. The oil-soluble sul-' M fonates maybeseparately recovered and purified by various means.

One suitable method for obtaining the purified sulfonates from thissolution will be described. The solution is made neutral tophenolphthalein with sulfuric acid or carbon dioxide in order to 40neutralize any residual free alkali. The solution is then dehydrated bycontacting with an agent at least equivalent in dehydrating power tosodium carbonate mono-hydrate, in sufficient quantity to substantiallydehydrate'the alcohol. This 45 usually requires from two to four poundsof the carbonate per gallon of water in the alcohol solution treated.The temperature of treating is preferably above 32 C., the melting pointof the polyhydrate salts formed. The mixture is agitaited thoroughly andthen settled, and the reany specific examples which have been presentedherein solely for purpose of illustration, but only by the followingclaims in which it is desired to claim all novelty insofar as the priorart permits.

I claim:

1. Germicidal and antiseptic composition comprising a solution in awater-soluble solvent of an alkyl phenol and-an oil-soluble sulfonatederived from petroleum oils, said solution being miscible in waterWithout appreciable formation of a separate phase.

2. Germicidal and antiseptic composition mis cible with largeproportions of water without appreciable formation of a separate phase,comprising isopropyl alcohol containing in solution an oil solublesulfonate derived from petroleum oils and an. alkyl phenol having 4 to10 carbon atoms in alkyl groups.

3. Germicidal and antiseptic composition comprising a solutioncontaining 1 to 10% secondary hexyl phenol and 2 to 20% oil solublesulfonate derived from petroleum oils in isopropyl alcohol,

said solution being diluted with up to about fifty parts of water. I

4. ,Germicidal and antiseptic composition comprising a substantiallyclear aqueous composition containing a major proportion of water, anoilsoluble sulfonate derived from petroleum oils, a water-insolublealkyl phenol in an effective amount, and a water-soluble solvent forsaid sulfonate and said alkyl phenol.

REUBEN SCHULER.

